Organic mercury compound.



. Charlottenburg, near Berlin,

HEINRICH SGHOT'I',v OI GHABLOTTENBURG,

GERMANY, assrenon r0 scrum. onsnnn- SGHAFT FUR-ANILIN FABRIKATION, OF BERLIN, GERMANY..

ORGANIC MERCURY COMPOUND.

1,016,784. 110 Drawing.

I Specification of Letters Patent.

Application filed Kay 8, 1911. Serial No. 625,770.

' Patented Feb. 6, 1912.

To all whom it mag concern:

Be it known that I, HmNnIou SoHo'rr, a citizen of the German Empire, residing at Charlottenburg, near Berlin, Germany, my post-ofiice address being Eichenallee 35, Germany, have invented certain new and useful Improvements in New Organic Mercury Compounds, of which the following is a specification. v 0

Among the great number of organic mercury compounds which are employed for internal or external medicinalpurposes and as germicides a special kind of such compounds has become of great importance which contain the mercury bound in such a way that it is not ionized in an aqueous solution of such a compound.

Now my present invention relates to a new class of this kind of mercury compounds which is derived from pyrazolones having, according to the commonly used constitution formula, a free methylene group: CH,, and more especially from phenylpyrazolones, such asfor instance 1- phenyl-3-methyl-5-pyrazolone, '1-phenyl-3- methyl-5-pyrazolone sulfonic acids, phenyl pyrazolone carboxylic acids, nitroor ammophenylpyrazolones, phenylpyrazolone-methylamino-omega-carboxylic aclds etc. The mercurized bodies of this new series which are soluble in water, for instance those which contain a sulfonic or carbolx'ylic group, are especially suitablelfor medicinalpurposes. Researches as to the question of the germicidal power of these soluble mercury compounds have been very satisfying; for instance it has been found that a mercury compound which is obtained from 1- phenyl-3-methyl-5 -pyrazolone-para-sulfonic acid and which contains about 27% of mercury is nearly as germicidal as mercuric chlorid.

' In order to obtain my new mercury compounds one may proceed in different ways. For instance a pyrazolone compound having amethylene group: --OH, such as for instance 1 phenyl 3 methyl 5 pyrazolone Y may be dissolved in water with the addition of a caustic alkali and may be brought in reaction with an inorganic or organic mercuric salt or compound, such as for instance mercuric chlorid, mercuric acetate, mercuric oxid, themercury compounds of alanin, of

glycocoll, of acetamid, etc. .Of course if a kali salt. In this way very valuable new I mercury compounds can be manufatured.

The following examples may' serve to illustrate my invention, the parts being by weight 1. 17.4 parts of l-phenyl-3-methyl-5 pyra zolone are dissolved in about 200 parts of water with the addition of 12.5 partsof sodalye of 40 Baum specific gravity. The solution thus obtained is added to an aqueous solution of 13.6 parts of mercuric chlorid; it separates at once a thick white precipitate which is isolated by draining, washing with water and drying. The new mercury compound thus obtained melts at about 220 C.

and 1s decomposed when heated above this point. It is very diflicultly soluble in water and when acted upon with soda-lye even at, the boil no yellow mercuric oxid is formed. The new body is easily soluble in, benzene and rather soluble in glacial acetic acid but very difiicultly solublein alcohol and acetone.

If in the foregoing example the proportion of mercuric chlorid is doubled, that is to say if 2 molecular proportions of mercuric chlorid are employed to 2 molecular proportlons of the pyrazolone derivative, a

newmercury compound is obtained which contains the mercury also in the form not capable of ionization. This product is also very difiicultly soluble in water, but easily soluble in benzene and very easily soluble in acpltone. On heating it melts at about 190 I 2. A freshly prepared paste of mercuric oxid which is prepared by dissolving 16.3 parts of mercurlc chlorid in water, filtering the aqueous solution into diluted soda-lye and washing carefully the mercuric oxid thus precipitated, is added while heating and agitating to a solution of 15 parts of 1-phenyl-3-methyl-5-pyrazolone in about 200 rated. This. product is easily soluble in erties -it seems that this compound is not go of such a quantity. of calcined sodium car- I which is prepared by'dissolving 27 parts of I Thus is obtained ,the new mercury compound 65. turmg the mercury compounds of such other parts of acetone. The mercuric oxid enters Into solution quickly. z This point attalned, the solution is filtered if necessary evaporated preferably in vowe and pulverized. 5 Thus is obtained a new mercury compound .in the shape of a slightly yellowish po'w'der flpossessing a high percentage of. mercury and from which even on heating for a long time with soda-lye no mercuric oxid is-sepaacetone, benzene and glacial acetic acid and rather'soluble' in alcohol. On heating it melts'at about 170 and byfurther heating it is decomposed. Accordmg to these propidentical with that of the Example 1.-

3. 51 parts of 1-phenyl-3-methyl-5-pyrazo-- lone-para-sulfonic acid are dissolved in about 500 parts of water with the addition bonate that aneutral or weaklyalkaline solution isobtained. This solution, after filterin if necessary, is introduced into a fresh y prepared paste of mercuric oxid mercuric chlorid in water, filtering this solution into an excess of dilute soda-lye and washing the mercury oxid with water. This mixture is then heated gently while agitat- 30 ing, the mercuric oxid dissolving within a short time. This point being attained the solution is filtered if necessary and the filtered solution is evaporated using a highly diminished ressure and a low temperature.

I in the shape of a weakly yellow colored pow der which is easily soluble in water to a yellow solution, from this solution on the addition of soda-lye no separation of mercuric 40 oxid occurs. On heating the new substance assumes a dark color at about 200 C. and on further heating up to 360 no visible decomposition occurs. This new com ound contains about 27% of mercury an according to special researches this new mercury compound has been proved to benearly asgermicidal as mercuric chlorid.

It is obvious to those skilled in the art that my present invention is not limited to the foregoing examples or to the details given therein. For example, instead of 1 phenyl 3 methyl 5 e pyrazolone nitro-, am1do-, chlorobromoand other" derivatives of this henylpyrazolone derivative 5 and having a so-called free 4-position may be used; likewise for the 1-phenyl-3-methyl-5- pyrazolone-para-sulfonic acid another sulfonic acid, as for instance the meta-sulfonic acid or a chloro-sulfonic acid, such as for instance, -ortho-chloro-1-phenyl-3-methyl-5- pyrazolone-meta-sulfonic acid (Cl :NH :SO,H=1 :2 :4.) may be substituted. Of course if manufac- H pyrazolone derivatives thespecial conditions reaction may bevaried in order to obtain the best results.

Thegermicidalower of the new mercury compounds as we as their efliciency as internal remedies naturally depend to a certain extent upon the proportion of mercury contalnedtherein; in th1s respect it is convenientto state that'various quantities of mercury canbe introduced into the molecule of the respective organic compound by employing difierent pro ortions of mercuric chlorid or mercuric oxi or of another mercury compound in respectto the proportion of the organic compound in question.

Finally a number of 1pyrazolone compounds maybe named whic are also adapted to the manufacture of my new mercury'compounds, namely 1-phenyl-3-methyl-5-pyi'av zolone-parai-methylamino-omega carboxyhc .acid, 1-phenyl-3-pyrazolone, 3-phenylgyrazolone, py azolone -3 carboxyhc ac1 1- phenyl 5 yrazolone 3 carboxylic acid, 1- phenyl 2 ethyl-5-pyrazolone, 1-phenyl-2- methyl 5 pyrazolone 3-methyl-carboxylic acid, 1 phenyl 3 pyrazolone-2-urethane, 1- phenyl-5-methyl-3-pyrazolone, 1.2-diphenyl- '3 methylpyrazolone, 1.5-diphenyl-3-pyrazolone, 1-phenyl-5-pyrazolone, etc. I

'Having now described my invention and the manner in which it may be performed, what I claim is,

1. The'hereinbefore-described process for the manufacture of new organic mercury .compounds whlch consists 1n acting with a mercury compound on a pyrazolone which, according to the commonly employed constitution formula, contains a methylene group:

2: The hereinbefore-described process for the manufacture of new organic mercury compounds which consists in acting with a mercury compound on a phenylpyrazolone which, according to the commonly em loyed constitution formula, contains a met ylene group: GH,--.

3. The hereinbefore-described process for the'manufacture of new organic mercury compounds which consists in acting with a mercury compound on 1-phenyl-3-methyl-5- pyrazolone-para-sulfonic acid.

4. The hereinbefore-described process for the manufacture of new orgamc mercury compounds which consists inacting with mercuric oxid on a solution of an alkali salt of 1-phenyl-3-methyl-5-pyrazolone-para-sulfonic acid.

5. The hereinbefore-described process for the manufacture of a new orgamc mercury compound which consists in acting with the mercuric oxid prepared from 27 parts of mercuric chlorid on an aqueous solution of the normal sodium salt lprepared from 51 parts of 1 phenyl- 3 met yl 5 -pyrazolonepara-sulfonic acid.-

6. As new articles of manufacture new orgamc mercury compounds contammg a 'pyrazolone residuefwhich pyrazolone resi due in the free state, according to the commonly used constitution formuIa, possesses a methylene group; -CH which new compounds cofi'tain the mercury bound in such a way that it is not capable of ionization, and from which compound by the action of caustic alkali no mercuric oxid is separated, but which new compounds by the action of a mineral'acid are split up, the mercury being eliminated from the organic residue of the molecule, and these new compounds when heated in a current of coal-gas in mixture with calcium oxid being decomposed so that metallic mercury distils over, and which new mercury compounds show a strong germicidal power and possess a high melting point or point of decomposition.

7. As new articles of manufacture new organic mercury compounds containing a phenylpyrazolone residue, which phenylpyrazolone residue in the free state, according to the commonly used constitution formula, possess a methylene group: -CH which new compounds contain the mercury bound in such a way that it is not capable of ionization, and from which compound by the action of caustic alkali no mercuric oxid is separated, but which new compounds by the action of a mineral acid are split up, the mercury being eliminated from the organic residue of the molecule, and these-new compounds when heated in a current of coalgas in mixture with calcium oxid being decomposed so that metallic mercury distils over, and which new mercury compounds show a strong germicidal power and possess a high melting point or point of decomposition.

8. As new articles of manufacture the new organic mercury compounds containing mercury in association with l-phenyl-S-methyl- 5-pyrazolone-para-sulfonic acid, in which new compounds the mercury is not-capable of ionization and from which new mercury compounds by the action ofcaustic alkali no compounds by the action of a mineral acid are split up,.the mercury being eliminated from the organic residue of the molecule, and these new compounds when heated in a current of coal-gas in mixture with calcium oxid being decomposed so that metallic mercury distils over, and which new mercury compounds show-a strong germicidal power and possess a high point of decomposition.

9. As a new article of manufacture the new organic mercury compound containing 'mercury in association with 1-phenyl-3- mercuric oxid is delivered, but which new 7 new compound by the action of a mineral acid being split up, the mercury being eliminated from the organic residue of the'molecule, and this new compound when heated in a current of coal-gas in mixture with calcium oxid being decomposed so that metallic mercury distils over, and which new mercury. compound possesses a high point of decomposition.

In testimony whereof I have hereunto set my hand in presence of two subscribing wltnesses.

HEINRICH SCHOTT.

Witnesses WOLDEMAR HAUPT, HENRY HASPER. 

